US10752969B2 - Steel for suspension spring and method of manufacturing same - Google Patents
Steel for suspension spring and method of manufacturing same Download PDFInfo
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- US10752969B2 US10752969B2 US15/537,578 US201615537578A US10752969B2 US 10752969 B2 US10752969 B2 US 10752969B2 US 201615537578 A US201615537578 A US 201615537578A US 10752969 B2 US10752969 B2 US 10752969B2
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 162
- 239000010959 steel Substances 0.000 title claims abstract description 162
- 239000000725 suspension Substances 0.000 title claims abstract description 105
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- 229910000734 martensite Inorganic materials 0.000 claims abstract description 61
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/02—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the present invention relates to a steel for a suspension spring which is used in a suspension spring of a vehicle or the like and a method of manufacturing the same.
- Priority is claimed on Japanese Patent Application No. 2015-046915, filed on Mar. 10, 2015, the content of which is incorporated herein by reference.
- a suspension spring for a vehicle is the largest spring among the springs used in a vehicle, and is a relatively heavy component. Therefore, from the viewpoint of improving fuel efficiency of the vehicle, weight reduction is required.
- the weight reduction of the suspension spring contributes to reducing the weight of a so-called unsprung weight. When it is possible to reduce the unsprung weight, it becomes advantageous absorb of shock which the vehicle receives from a road surface during traveling, and thus, the weight reduction of the suspension spring contributes improve a ride quality of the vehicle, and improve grounding properties or stability and controllability during the traveling.
- the tensile strength of the suspension spring used in the vehicle is approximately 1800 MPa, but it is necessary to further increase the strength of the suspension spring in order to reduce the weight.
- the suspension spring for a vehicle is manufactured by quenching and tempering. Therefore, a structure thereof is tempered martensite which is a structure obtained as martensite receives tempering. It is known that steel having such a structure in which a prior austenite (hereinafter, prior ⁇ ) boundary is embrittled when hydrogen infiltrates into the steel, and as a result, a brittle fracture is caused at a stress that is equal to or less than a yield strength of the steel. In addition, it is known that the brittle fracture is likely to occur at a low stress at a small amount of hydrogen as the strength of the steel increases.
- prior ⁇ prior austenite
- the suspension spring is generally used in a state of being coated, and infiltration of hydrogen into a coated part is suppressed.
- the coating may be damaged by a stone chip or contact between wires of the spring while the vehicle travels.
- corrosion may occur from the part, and a part of hydrogen generated according to a corrosion reaction infiltrates into the steel. Therefore, even in a case of steel for a suspension spring used being coated, in order to increase the strength, it is necessary to take a measure against hydrogen embrittlement.
- Patent Document 1 and Patent Document 2 steel for a high strength spring in which fatigue properties or delayed fracture resistance properties when the hydrogen is stored in the steel are improved by setting an aspect ratio of a prior ⁇ grain to be 1.5 to 2, is suggested.
- Patent Document 3 and Patent Document 4 similar to the steel for a suspension spring, a technology of controlling the aspect ratio of the prior ⁇ grain with respect to steel bars for prestressed concrete (a member manufactured by quenching and tempering among tendons for prestressed concrete (PC)) by which hydrogen embrittlement resistance (delayed fracture resistance properties) is improved, is suggested.
- Patent Document 1 to Patent Document 4 obtains martensite which is rapidly cooled from a state of unrecrystallized ⁇ at a surface part of a wire rod, that is, a martensite structure having a prior ⁇ grain which stretches in a longitudinal direction of the wire rod, by controlling the temperature of finish rolling to be lower than a normal temperature and by performing quenching immediately after the finish rolling, in hot working in a ⁇ (austenite) region.
- the treatment can be realized when a dedicated manufacturing line for manufacturing a steel wire of steel for a spring, using a hot rolled wire rod as a material.
- Wire rod rolling is multi-stage processing in which reduction of area is large. Therefore, since the ⁇ (austenite) is rolled into a shape of a wire rod while repeating recrystallization, a ⁇ grain size becomes fine. When the ⁇ grain size is fine, the recrystallization is likely to occur after the finish rolling. Since the ⁇ after the recrystallization has a shape which is close to a spheroidal shape, in the wire rod rolling, it is difficult to obtain the stretched unrecrystallized ⁇ .
- quenching cracks are likely to be generated.
- the quenching cracks are likely to be generated in a case where cooling during the quenching is ununiform. While it is possible to perform the cooling relatively uniformly in a case of performing the rapid cooling in a state of a wire rod, it is difficult to uniformly cool the coil due to a difference in position between an overlapping part and a non-overlapping part of the wire rod or between an upper part and a lower part of the coil, and ununiformity of a flow of a quenching medium in the cooling bath in a case of performing the rapid cooling in a state of a coil wound after the wire rod rolling. Therefore, in a case of rapidly cooling the coil by the general-purpose wire rod rolling line, it is necessary to pay attention to the quenching cracks.
- the general-purpose wire rod rolling line for example, that manufactures the hot rolled wire rod using a steel piece as a material
- Patent Document 1 Japanese Patent (Granted) Publication No. 4116762
- Patent Document 2 Japanese Unexamined Patent Application, First Publication No. 2014-43612
- Patent Document 3 Japanese Patent (Granted) Publication No. 3153072
- Patent Document 4 Japanese Patent (Granted) Publication No. 3217589
- a steel composition and a rolling condition for suppressing the recrystallization of ⁇ during the period from finish rolling and winding to rapid cooling in wire rod rolling a steel composition and a rolling condition for suppressing the precipitation of a during the period from the finish rolling and the winding to the rapid cooling, and a steel composition and a cooling condition for preventing the quenching cracks during the rapid cooling, were investigated.
- the main idea of the present invention is as follows based on the above-described knowledge.
- steel for a suspension spring as a chemical composition, by % by mass: C: more than 0.40% and 0.65% or less; Si: 1.00% to 3.50%; Mn: more than 2.00% and 3.00% or less; Cr: 0.01% to 2.00%; V: 0.02% to 0.50%; Al: 0% to 0.060%; Mo: 0% or more and less than 0.50%; Cu: 0% to 1.00%; Ni: 0% to 1.50%; Nb: 0% to 0.015%; Ti: 0% to 0.200%; B: 0% to 0.0050%; P: limited to 0.020% or less; S: limited to 0.020% or less: N: limited to 0.0100% or less; and a remainder of Fe and impurities, in which Kf defined by the following Equation (a) is 280 or more, in which a structure contains a tempered martensite of which an area ratio is 90% or more, in which a Fe-based carbide precipitated in the tempered
- C (%), Si (%), Mn (%), Ni (%), Cr (%), Cu (%), and Mo (%) in the equation (a) indicate the amounts of C, Si, Mn, Ni, Cr, Cu, and Mo by % by mass, and in a case where the elements are not contained, the value is 0.
- the steel for a suspension spring according to (1) may include, as a chemical composition, by % by mass: one of or two or more of Mo: 0.02% or more and less than 0.50%; Cu: 0.02% to 1.0%; Ni: 0.02% to 1.5%; and Nb: 0.002% to 0.015%.
- the steel for a suspension spring according to (1) or (2) may include, as a chemical composition, by % by mass: one of or both of Ti: 0.010% to 0.200%; and B: 0.0005% to 0.0050%, in which the amount of Ti and the amount of N satisfy Ti ⁇ 3.5 ⁇ N.
- a method of manufacturing the steel for a suspension spring including: heating a steel piece containing the chemical composition within a temperature range of 950° C. or more and less than 1150° C.; a wire rod rolling including a finish rolling in which a reduction of an area is 30% or more and a finish rolling temperature is 750° C. to 850° C., with respect to the heated steel piece to obtain a wire rod; winding with respect to the wire rod to make the wire rod into a coil; cooling the coil so as to start cooling in 5 to 30 seconds after the performing of the winding and to set an average cooling rate when the temperature is 800 to 300° C. to be 5 to 50° C./s to cool the coil until reaching 300° C. or less; and tempering of retention for 10 to 1800 seconds at 410° C. to 500° C. after the cooling.
- the steel for a suspension spring which has a high strength in which a tensile strength is 1900 MPa or more and excellent hydrogen embrittlement resistance.
- FIG. 1 is a view showing a shape of a test piece of a delayed fracture test.
- FIG. 2 is a view showing an example of a measuring position of an area ratio of a stretched prior ⁇ grain on a section of steel for a suspension spring.
- the steel for a suspension spring according to the embodiment has the following characteristics.
- C (%), Si (%), Mn (%), Ni (%), Cr (%), Cu (%), and Mo (%) in the Equation (1) indicate the amounts of C, Si, Mn, Ni, Cr, Cu, and Mo by % by mass, and in a case where the elements are not contained, the value is 0.
- a structure contains tempered martensite of which an area ratio is 90% or more.
- Fe-based carbide precipitated in the tempered martensite is cementite.
- the average of area ratios of prior austenite grains which stretch in a longitudinal direction of the steel and of which an aspect ratio exceeds 3.0, is 80% or more in a case of depths of 0.1 mm, 0.2 mm, and 0.3 mm in a sheet thickness direction from a surface of the steel.
- % regarding the chemical composition indicates % by mass.
- C is an element necessary for improving the strength of the steel containing the tempered martensite.
- the lower limit of the amount of C is preferably 0.50%.
- the upper limit of the amount of C is 0.65%.
- the upper limit of the amount of C is preferably 0.60%.
- Si is an element which is extremely efficient in improving resistance to temper softening of the tempered martensite steel similar to the steel for a suspension spring.
- Si is an element which is also efficient in improving settling resistance of the spring.
- the lower limit of the amount of Si is preferably 1.20%.
- the upper limit of the amount of Si is set to be 3.50%.
- the upper limit of the amount of Si is preferably 2.50%, and the upper limit is more preferably 2.00%.
- Mn is an important element in the steel for a suspension spring according to the embodiment.
- it is efficient to lower a finish rolling temperature.
- ⁇ receives multi-stage processing, and the recrystallization is repeated, the ⁇ grain size becomes fine.
- the recrystallization is likely to occur after the finish rolling, and thus, it is difficult to obtain the unrecrystallized ⁇ .
- the temperature region in which the ⁇ transformation is started is lowered due to an increase in Mn, the transformation start time moves to a long time side, and thus, it is advantageous to suppress the ⁇ transformation.
- the amount of Mn exceeds 2.00%.
- the lower limit of the amount of Mn is preferably 2.10%, the lower limit of the amount of Mn is more preferably 2.20%, and the lower limit is still more preferably 2.30%.
- the upper limit of the amount of Mn is set to be 3.00%.
- the upper limit of the amount of Mn is preferably 2.60%.
- Cr is an element efficient for improving hardenability or improving resistance to temper softening of the steel for a suspension spring.
- the lower limit of the amount of Cr is preferably 0.20%.
- the upper limit of the amount of Cr is set to 2.00%.
- the upper limit of the amount of Cr is preferably 1.00%.
- V is an important element in the steel for a suspension spring according to the embodiment.
- it is efficient to lower the finish rolling temperature.
- the ⁇ grain size becomes fine.
- it requires time to the rapid cooling after the finish rolling. Therefore, when the finish rolling temperature is lowered, the recrystallization is likely to occur during the period from the finish rolling to the rapid cooling, and it is difficult to obtain the unrecrystallized ⁇ .
- the finish rolling temperature it is required to set the finish rolling temperature to be lower than that of the general operating condition, but when the finish rolling temperature becomes excessively low, miss roll is likely to be generated. Since V is extremely efficient in suppressing the recrystallization of ⁇ , by containing V, it is possible to stably obtain the unrecrystallized ⁇ for a long period of time in a general low temperature finish rolling condition, and it is possible to avoid excessive low finish rolling temperature. In order to obtain the above-described effect, it is necessary to set the lower limit of the amount of V to be 0.02%.
- the lower limit of the amount of V is preferably 0.05%, and the lower limit of the amount of V is more preferably 0.10%.
- the upper limit of the amount of V is set to be 0.50%.
- the upper limit of the amount of V is preferably 0.20%.
- P is an impurity, and is an element which embrittles the prior ⁇ boundary and deteriorates delayed fracture resistance properties (hydrogen embrittlement resistance). Therefore, it is necessary to limit the amount of P to be 0.020% or less. The amount of P is preferably limited to 0.015% or less.
- S is an impurity, and is an element which embrittles the prior ⁇ boundary and deteriorates delayed fracture resistance properties (hydrogen embrittlement resistance). Therefore, it is necessary to limit the amount of S to be 0.020% or less.
- the amount of S is preferably limited to 0.015% or less, and is more preferably limited to 0.006% or less.
- N is an impurity, and is an element which deteriorates hot rolling of the steel and damages manufacturability during continuous casting. Therefore, it is necessary to limit the amount of N to be 0.0100% or less. The amount of N is preferably limited to 0.0070% or less.
- the steel for a suspension spring according to the embodiment basically contains the above-described chemical composition and the remainder of Fe and impurities.
- the impurities mean composition mixed from a raw material, such as ore or scrap, and due to other reasons.
- one of or two or more of Al, Mo, Cu, Ni, and Nb may further be contained with the range which will be described later. However, since the elements are not necessarily contained, the lower limits thereof are 0%.
- Al is an element efficient in deoxidizing the steel.
- the deoxidation is performed by Si
- Al may not be necessarily contained, but in a case where the deoxidation is performed by Al, 0.010% or more of Al is preferably contained.
- the amount of Al exceeds 0.060%, a problem, such as deterioration of toughness due to generation of coarse inclusion, becomes serious. Therefore, even in a case of containing Al, the upper limit of the amount of Al is set to be 0.060%
- Mo is an element which contributes to improving hardenability of the steel with a small amount thereof.
- Mo is efficient in suppressing the recrystallization of the processed ⁇ , and has a function of complementing the effect of suppressing the recrystallization of the processed ⁇ by containing the V.
- the amount of Mo is preferably set to be 0.02% or more.
- the amount of Mo is more preferably 0.05% or more.
- Mo is an expensive alloying element, it is disadvantageous from the viewpoint of manufacturing costs when the amount of Mo becomes 0.50% or more. Therefore, even in a case of containing Mo, the amount of Mo is set to be less than 0.50%.
- the amount of Mo is preferably 0.30 or less.
- Cu is an element which improves corrosion resistance. In a case of obtaining the above-described effect, it is necessary to set the amount of Cu to be 0.02% or more.
- the amount of Cu is preferably 0.05% or more. Meanwhile, when the amount of Cu exceeds 1.00%, a problem that the hot rolling of the steel deteriorates, cracks or surface imperfections are generated during the continuous casting, and manufacturing yield deteriorates, becomes serious. Therefore, even in a case of containing the Cu, the amount of Cu is set to be 1.00% or less.
- the amount of Cu is preferably 0.20% or less.
- Ni is an element which improves corrosion resistance, and is an element efficient in improving toughness. In a case of obtaining the above-described effect, it is necessary to set the amount of Ni to be 0.02% or more.
- the amount of Ni is preferably 0.10% or more. Meanwhile, since Ni is an expensive alloying element, it is disadvantageous from the viewpoint of manufacturing costs when the amount of Ni exceeds 1.50%. Therefore, even in a case of containing Ni, the amount of Ni is set to be 1.50% or less.
- the amount of Ni is preferably 0.50% or less.
- Nb is an element efficient in suppressing the recrystallization of the processed ⁇ , and has a function of complementing the effect of suppressing the recrystallization of the processed ⁇ by containing V.
- the amount of Nb is preferably set to be 0.002% or more.
- the amount of Nb is more preferably 0.005% or more.
- the amount of Nb exceeds 0.015%, a problem not only that the effect is saturated but also that cracks or surface defects are generated during the continuous casting and manufacturing yield deteriorates, becomes serious. Therefore, even in a case of containing the Nb, the amount of Nb is set to be 0.015% or less.
- the amount of Nb is preferably 0.010% or less.
- the steel for a suspension spring according to the embodiment may further contain one or both of Ti and B within the following range as necessary. However, since the elements are not necessarily contained, the lower limits thereof are 0%.
- Ti is an element efficient in suppressing the recrystallization of the processed ⁇ , and has a function of complementing the effect of suppressing the recrystallization of the processed ⁇ by containing V.
- Ti is an element efficient in ensuring the amount of solid solution B.
- the amount of Ti is preferably 0.015% or more.
- the amount of Ti is set to be 0.200% or less.
- the amount of Ti is preferably 0.100% or less.
- B is an element which contributes to improving the hardenability of the steel with a fine amount thereof.
- B has an effect of suppressing grain boundary fracture by segregating into the prior ⁇ grain and strengthening the prior ⁇ boundary.
- the amount of B is preferably 0.0005% or more.
- the amount of B is more preferably 0.0010% or more.
- B forms a precipitate, such as BN or Fe 23 (C,B) 6 , and on the contrary, deteriorates a grain boundary strength. Therefore, even in a case of containing B, the amount of B is set to be 0.0050% or less.
- the amount of B is preferably 0.0030% or less.
- the quenching cracks are likely to be generated when transforming the martensite by performing the rapid cooling with respect to the wire rod.
- the quenching cracks are likely to be generated.
- ⁇ is precipitated during the cooling when lowering the cooling rate, and it is not possible to obtain necessary tempered martensite fracture (area ratio) as the steel for a suspension spring.
- ⁇ is precipitated during the cooling when lowering the cooling rate, and it is not possible to obtain necessary tempered martensite fracture (area ratio) as the steel for a suspension spring.
- Kf defined by the following Equation (1)
- a preferable range of Kf is 300 or more.
- Kf is preferably set to be 10000 or less.
- Kf 10 (3.288 ⁇ C (%) ⁇ 0.168 ⁇ Si (%)+1.068 ⁇ Mn (%)+0.3 ⁇ Ni (%)+1.266 ⁇ Cr (%)+0.626 ⁇ Cu (%)+2.086 ⁇ Mo (%) ⁇ 1.931) (1)
- C (%), Si (%), Mn (%), Ni (%), Cr (%), Cu (%), and Mo (%) in the Equation (1) respectively indicate the amounts of C, Si, Mn, Ni, Cr, Cu, and Mo by % by mass, and in a case where the elements are not contained, the value is 0.
- the spring Since the spring is a mechanical element that uses a restoring force as an elastic body, and accumulates elastic energy, the spring is necessary the large yield strength. Therefore, in the steel for a suspension spring, it is necessary to use the tempered martensite which can obtain a high yield strength and has excellent toughness as the main structure.
- the proportion of the tempered martensite in the structure is set to be 90% or more by the area ratio. When the area ratio of the tempered martensite is less than 90%, it is not possible to sufficiently ensure both of strength and toughness.
- the area ratio of the tempered martensite is 90% or more, as a remainder, one or more of ferrite, pearlite, bainite, or residual austenite may also be contained. However, it is desirable to reduce the area ratio of the structure other than the tempered martensite as much as possible.
- the total area ratio of one or more of ferrite, pearlite, bainite, and residual austenite is preferably 5% or less, that is, the area ratio of the tempered martensite is preferably 95% or more.
- the remainder may be 0%, and in this case, the area ratio of the tempered martensite is 100%.
- the steel for a suspension spring according to the embodiment, by performing the evaluation, it is possible to evaluate the area ratio of the tempered martensite as a representative area ratio in the entire steel.
- the Fe-based carbide is precipitated.
- the Fe-based carbide in the tempered martensite is cementite ( ⁇ ).
- ⁇ cementite
- hydrogen embrittlement resistance of ⁇ is inferior to that of ⁇ , in a case where c is precipitated as the Fe-based carbide, it is not possible to obtain sufficient hydrogen embrittlement resistance.
- Identification of the Fe-based carbide can be performed by the following method.
- the fracture in the prior ⁇ boundary is generated starting a defect caused by corrosion in a case of the suspension spring manufactured by the steel for a suspension spring.
- the prior ⁇ grain boundary fracture is generated from the surface layer of the suspension spring. Therefore, in order to suppress the prior ⁇ grain boundary fracture generated from the surface layer of the suspension spring, it is extremely important to stretch the prior ⁇ grain of the surface layer of the steel for a suspension spring in the longitudinal direction of the steel for a suspension spring. In addition, it is efficient to stretch the prior ⁇ grain of the surface layer of the wire rod which is a material of the steel for a suspension spring for suppressing the prior ⁇ grain boundary fracture in the longitudinal direction of the wire rod.
- the proportion of the prior ⁇ grain size having a large aspect ratio increases, the effect is stably obtained.
- the inventors have found that it is necessary the prior ⁇ grain size in which the aspect ratio exceeds 3.0 to set to be 80% or more by the area ratio among all of the prior ⁇ grains in order to stably obtain the above-described effect.
- the aspect ratio of the prior ⁇ grain size is preferably 3.5 or more.
- the inventors have found that the effect of suppressing the prior ⁇ grain boundary fracture is not sufficient when the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 is 80% or more on average in the range from the surface of the steel to a depth of 0.3 mm. It is considered that this is because a certain proportion or more of the prior ⁇ grain having a large aspect ratio is necessarily present to the position (depth) that is not influenced by the corrosion from the surface of the steel since the defect caused by the corrosion is a starting point of the prior ⁇ grain boundary fracture due to hydrogen embrittlement in the steel for a suspension spring.
- the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 in the range from the surface of the steel to 0.3 mm is a value obtained by measuring the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 and averaging the area ratios, on a straight line oriented toward the center of a steel for a suspension spring 1 from the surface of the steel for a suspension spring 1 , and in each of a position 11 having a depth of 0.1 mm, a position 12 having a depth of 0.2 mm, and a position 13 having a depth of 0.3 from the surface of the steel for a suspension spring 1 .
- the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 is preferably 80% or more.
- the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 is preferably 85% or more.
- the aspect ratio is obtained by measuring at least 15 or more grains at each of the measuring positions and averaging the values.
- the steel for a suspension spring according to the embodiment can be manufactured by the method of manufacturing including the following processes.
- the method of manufacturing can be realized by using the general-purpose wire rod rolling line.
- the steel for a suspension spring As a material of the steel for a suspension spring according to the embodiment, it is possible to use a steel piece which has the above-described chemical composition and is manufactured via a general steel manufacturing process and a blooming process.
- the steel piece is made in a shape of a wire rod by performing the hot rolling, the steel piece is heated to the ⁇ region.
- the heating temperature is preferably 1000° C. or more.
- the steel piece is decarburized. The decarburized layer of the surface layer formed in a stage of the steel piece is taken over to the suspension spring manufactured by the wire rod obtained by rolling the steel piece, the steel for a suspension spring obtained by tempering the wire rod, and the steel for a suspension spring, and causes deterioration of fatigue strength of the suspension spring. Therefore, it is necessary to set the heating temperature of the steel piece to be less than 1150° C.
- the heating temperature is preferably 1100° C. or less.
- the steel piece is formed in a shape of a wire rod by performing the wire rod rolling including rough rolling, intermediate rolling, and finish rolling with respect to the heated steel piece.
- the steel for a suspension spring according to the embodiment stretches the ⁇ grain of the surface part of the steel in the longitudinal direction in the finish rolling. In order to obtain the prior ⁇ grain having a desirable aspect ratio, in the finish rolling, it is necessary to set the reduction of area to be 30% or more. The reduction of area is preferably 40% or more.
- the finish rolling temperature decreases, the recrystallization of the processed ⁇ is suppressed. Therefore, in the manufacturing method of the steel for a suspension spring according to the embodiment, in order to obtain the prior ⁇ grain having a desirable aspect ratio, it is necessary to set the finish rolling temperature to be 850° C. or less.
- the finish rolling temperature is preferably 840° C. or less. Meanwhile, a problem that miss roll is likely to be generated when the finish rolling temperature is excessively low, or the like, becomes serious. Therefore, the lower limit of the finish rolling temperature is set to be 750° C. The lower limit is preferably 780° C.
- the wire rod is made into a coil (wire rod coil).
- the cooling starts in 5 to 30 seconds, and the quenching is performed by rapidly cooling the wire rod coil.
- the quenching for example, the wire rod made in a shape of coil is transported by using a conveyor, and is immersed into a cooling bath in which a medium (water or the like) for performing the rapid cooling after the transportation is kept.
- a medium water or the like
- the temperature range of 800° C. to 300° C. it is necessary to cool the temperature range of 800° C. to 300° C. until reaching 300° C. or less at 5° C./s or more of an average cooling rate.
- the cooling rate is preferably 10° C./s or more.
- the upper limit of the cooling rate is set to be 50° C./s.
- the upper limit of the cooling rate is preferably 40° C./s.
- a cooling stop temperature exceeds 300° C., the martensite is not sufficiently formed.
- the cooling rate in a case of immersing the wire rod coil into the cooling bath and rapidly cooling the wire rod coil can be controlled by changing the temperature of the cooling medium.
- a diameter of the wire rod is also a cause, but in a case of using water at a room temperature or oil having higher quenching capacity than that of the water as the cooling medium, there is a concern that the cooling rate of the wire rod coil exceeds 50° C./s, and thus, as the cooling medium, it is preferable to use water (warm water) having a temperature of 40° C. or more, and is more preferable to use water at 80° C. or more.
- the steel for a suspension spring according to the embodiment suppresses the recrystallization of ⁇ and the precipitation of a by V and Mn, and further ensures a certain degree or more of hardenability by setting Kf to be 280 or more, and thus, the average cooling rate of 800° C. to 300° C. may be 5° C./s.
- the cooling rate it is preferable to immerse the wire rod coil into the cooling bath, but when the cooling rate can be 5° C./s or more, the cooling may be performed by air blast cooling after the winding.
- the tempering is performed with respect to the wire rod to which the above-described heating process, the wire rod rolling process, the winding process, and the cooling process are performed.
- the temperature of the tempering can be appropriately changed in accordance with desirable properties, but it is preferable to perform the retention for 10 seconds to 1800 seconds within a range of 410° C. to 550° C. Furthermore, it is preferable to perform the retention for 10 seconds to 1800 seconds within a range of 430° C. to 520° C.
- tempering temperature is less than 410° C. since the Fe-based carbide is E main constituent.
- tempering temperature exceeds 550° C. is not preferable since there is a concern that ⁇ desirable tensile strength is not obtained.
- the steel wire (steel for a suspension spring) which is a material of a cold formed suspension spring is obtained.
- the method of manufacturing the steel for a suspension spring according to the embodiment may further include a temporary tempering process of performing temporary tempering with respect to the wire rod coil between the cooling process and the tempering process.
- the temporary tempering is efficient in preventing a season cracking of the wire rod, or in preventing disconnection during the straightening and the drawing by improving toughness or ductility.
- the above-described steel for a suspension spring can be processed to the suspension spring by a known processing method.
- converter ingot steel having the chemical composition (remainder is Fe and impurities) shown in Table 1 was performed the continuous casting to obtain a cast piece. Soaking and blooming were performed with respect to the cast piece as necessary, and a material (steel piece) for the wire rod rolling in which the section has an angle of 162 mm (length 162 mm ⁇ width 162 mm) was obtained.
- the steel piece was made into a wire rod having a diameter of 10 mm or 14 mm by performing the heating and the wire rod rolling under the condition shown in Table 2-1.
- the coil was transported to the cooling bath which is provided at a rear part of the rolling line for cooling the wire rod by a transport conveyor, and the quenching was performed by immersing the wire rod into the cooling bath after the transportation except for some of part of the wire rods.
- the wire rod is transported by the conveyor after being wound, and the time period until being immersed into the cooling bath was 16 seconds in any case.
- the cooling medium in the cooling bath water having a water temperature as described in Table 2-1 or medium oil was used.
- the wire rod which was immersed into the cooling bath was cooled until reaching the temperature which was substantially the same as the temperature of the cooling medium, and the wire rod which was not immersed into the cooling rod was cooled to 250° C. by the air blast cooling or by the air cooling after the winding.
- the temporary tempering was performed under the condition of retention for 30 minutes at 300° C. as necessary, and the straightening was performed.
- the drawing was performed with respect to the wire rod having a diameter of 14 mm to have a diameter of 13 mm and with respect to the wire rod having a diameter of 10 mm to have a diameter of 9.2 mm, and by performing the tempering at the temperature of Table 2-1, the wire for a spring (steel for a suspension spring) was obtained.
- the heating time of the tempering was 15 seconds.
- test piece for structure observation was collected from the wire for a spring manufactured in this manner.
- the structure observation was performed by using an optical microscope after performing polishing and etching a cut section of the test piece for structure observation which was collected by cutting the wire at the center part in the longitudinal direction. The result is shown in Table 2-2.
- the tempered martensite fraction was evaluated by acquiring the area ratios in each visual field by observing the surface part of 0.1 mm from the surface of the test piece to which nital etching was performed and each of the 3 visual fields at a 1 ⁇ 2 position of a radius from the surface at a magnification of 1000 times using an optical microscope, and by averaging the area ratios.
- the prior ⁇ grain was observed using the test piece to which the etching was performed by a solution obtained by adding a small amount of sodium dodecylbenzenesulfonate into a picric acid saturated aqueous solution, and the aspect ratio of the prior austenite grain from the surface layer to the depth of 0.3 mm and the area ratio of the prior austenite grain in which the aspect ratio exceeds 3.0 were measured.
- the observation using the optical microscope having a magnification of 1000 times was respectively performed in 5 visual fields, and after the observation, the aspect ratio of the prior ⁇ grain size and the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 are measured by the image analysis, and the average of 5 visual fields was considered as the aspect ratio of the prior ⁇ grain size at each position and the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0.
- the average of the area ratios of the prior ⁇ grain size in which the aspect ratio obtained at each position exceeds 3.0 was calculated, and the calculated average was considered as an average value of a prior ⁇ grain area ratio in which the aspect ratio from the surface layer to the depth of 3 mm exceeds 3.0.
- the Fe-based carbide in the tempered martensite was observed and measured by the following method. According to whether or not the heating peak was observed within the temperature range of 300° C. to 430° C. by the differential thermal analysis (Differential Scanning calorimeter: DSC), the presence and absence of the Fe-based carbides was confirmed, and by performing the restricted visual field electron beam diffraction pattern analysis by a thin film TEM observation, it was distinguished whether the Fe-based carbide is ⁇ or ⁇ .
- DSC Different Thermal analysis
- the tension test was performed using a round bar tension test in accordance with JIS Z 2201 and Z 2241. As a result of the tension test, when the tensile strength was less than 1900 MPa, it was determined that the strength was not sufficient.
- the delayed fracture test was performed in the following manner. In other words, using the test piece having a shape shown in FIG. 1 , after storing various amounts of hydrogen in the test piece in advance by electrolytic charging, and performing coating for preventing the hydrogen from escaping to the test piece, and after the coating, a constant load which was 0.3 times the tensile strength was applied. By performing the test with respect to the test piece charged by various amounts of hydrogen, a critical diffusible hydrogen content which was the upper limit of the amount of hydrogen by which the test piece did not cause the delayed fracture within 100 hours was measured. As a result of the delayed fracture test, it was determined that the delayed fracture resistance properties (hydrogen embrittlement resistance) deteriorates when the critical diffusible hydrogen content was less than 0.40 ppm.
- Cooling method (° C.) (° C.) A1-1 1 1050 40 800 14 30 Immerse into cooling tank 90 470 A1-2 1 950 40 800 14 30 Immerse into cooling bath 90 470 A1-3 1 1150 40 800 14 30 Immerse into cooling bath 90 470 A1-4 1 1050 30 800 14 30 Immerse into cooling bath 90 470 A1-5 1 1050 60 800 14 30 Immerse into cooling bath 90 470 A1-6 1 1050 40 750 14 30 Immerse into cooling bath 90 470 A1-7 1 1050 40 850 14 30 Immerse into cooling bath 90 470 A1-8 1 1050 40 800 14 5 Air blast cooling — 470 A1-9 1 1050 40 800 14 50 Immerse into cooling bath 40 470 A2 2 1050 40 800 14 30 30
- Cooling method (° C.) (° C.) B1-1 1 1200 40 800 14 30 Immerse into cooling bath 90 470 B1-2 1 1050 40 800 10 90 Immerse into cooling bath 40 470 B1-3 1 1050 40 800 14 2 Air cooling — 400 B1-4 1 1050 40 700 14 B1-5 1 1050 40 950 14 30 Immerse into cooling bath 90 470 B1-6 1 1050 40 900 14 30 Immerse into cooling bath 90 470 B1-7 1 1050 20 800 14 30 Immerse into cooling bath 90 470 B1-8 1 1050 40 800 14 100 Immerse into cooling bath Oil at 20° C.
- Manufac- Tempered surface layer in depth of 0.1 in depth of 0.2 in depth of 0.3 exceeds 3.0 from in depth of 0.5 turing martensite to depth of mm from surface mm from surface mm from surface mm from surface surface layer to mm from surface No.
- the area ratio of the tempered martensite was 90% or more, and the average value of the area ratios of the prior austenite grain in which the aspect ratio exceeds 3.0 was 80% or more from the surface layer to the depth of 0.3 mm.
- the tensile strength as the suspension spring was provided, the critical diffusible hydrogen content was 0.40 ppm or more, and the delayed fracture resistance properties were excellent.
- any of the chemical components, the area ratio of the tempered martensite, and the average value of the area ratios of the prior ⁇ grain in which the aspect ratio from the surface layer to the depth of 0.3 mm exceeds 3.0 was out of the range of the present invention.
- any of the tensile strength or the delayed fracture resistance properties deteriorated.
- B1-1 is an example in which a ferrite decarburized layer was generated in a range from the surface to 30 ⁇ m or more in the wire for a spring since the heating temperature during the rolling was excessively high.
- B1-2, B1-8, and B1-9 are examples in which the quenching cracks were generated in the wire rod and the wire for a spring could not be manufactured since the cooling rate during the rapid cooling after the wire rod rolling was excessive high.
- B1-3 is an example in which sufficient tempered martensite fraction was not obtained and the tensile strength was low since the cooling rate during the rapid cooling after the wire rod rolling was excessively low.
- B1-4 is an example in which miss roll was generated and the wire for a spring could not be manufactured since the finish rolling temperature during wire rod rolling was extremely low.
- B1-5 and B1-6 are examples in which ⁇ was recrystallized during the period from the winding to the quenching, and the area ratio of the prior ⁇ grain in which the aspect ratio exceeds 3.0 from the surface layer to the depth of 0.3 mm become low since the finish rolling temperature was excessively high.
- B1-7 is an example in which the area ratio of the prior ⁇ grain size in which the aspect ratio from the surface layer to the depth of 0.3 mm exceeds 3.0 become low since the reduction of area during the finish rolling was excessively small.
- the critical diffusible hydrogen content was low.
- B1-10 the critical diffusible hydrogen content was low since the tempering temperature was low and E precipitated as the Fe-based carbide.
- B31 is an example in which the retained ⁇ amount in which the amount of C was excessively large increases, the tempered martensite fraction was not sufficiently obtained, and the tensile strength was low.
- B32 is an example in which a tensile strength was not sufficiently obtained as the wire for a spring since the amount of C was excessively small.
- B33 is an example in which the quenching was not sufficiently performed and the tensile strength was low since the composition had a small Kf.
- B34 is an example in which resistance to softening during the tempering was small and the tensile strength was low since the amount of Si was excessively small.
- B35 is an example in which the ferrite transformation was started during the period from the winding to the quenching, the tempered martensite fraction was not sufficiently obtained, and the tensile strength was low since the amount of Mn was excessively small.
- B36 and B37 are examples in which the priory boundary was embrittled since the amounts of P and S was excessively large, and accordingly, are examples in which the critical diffusible hydrogen content was low.
- B39, B40, and B41 are examples in which the effect of suppressing the recrystallization was not obtained since the amount of V was excessively small or V was not contained, and accordingly the critical diffusible hydrogen content was low.
- the present invention it is possible to provide steel for a suspension spring which has a high tensile strength that is 1900 MPa or more, and excellent hydrogen embrittlement resistance.
- the steel for a suspension spring it is possible to increase the strength of a suspension spring, and thus, it is possible to contribute to reducing the weight of the suspension spring for a vehicle.
- a method of manufacturing a steel for a suspension spring of the present invention it is possible to manufacture the steel for a suspension spring having a high strength and excellent hydrogen embrittlement resistance by a general-purpose wire rod rolling line, and thus, it is possible to contribute to reduce the manufacturing costs.
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CN109082592B (zh) * | 2018-08-27 | 2020-08-18 | 河钢股份有限公司 | 一种综合性能良好耐腐蚀弹簧钢热轧盘条及其生产工艺 |
TWI747610B (zh) * | 2020-11-13 | 2021-11-21 | 中國鋼鐵股份有限公司 | 料倉秤重系統之檢測方法 |
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Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08311616A (ja) * | 1995-05-15 | 1996-11-26 | Sumitomo Electric Ind Ltd | 耐疲労性に優れたコイルばねとその製造方法 |
JPH09263876A (ja) * | 1996-03-29 | 1997-10-07 | Nippon Steel Corp | 遅れ破壊特性の優れた高強度機械構造用鋼およびその製造方法 |
JP2000256741A (ja) | 1999-03-09 | 2000-09-19 | Sumitomo Metal Ind Ltd | 熱間圧延棒鋼または線材の製造方法 |
JP2000256740A (ja) | 1999-03-09 | 2000-09-19 | Sumitomo Metal Ind Ltd | 熱間圧延線材の製造方法 |
JP3153072B2 (ja) | 1994-04-28 | 2001-04-03 | 新日本製鐵株式会社 | 耐遅れ破壊特性に優れた高強度鋼棒およびその製造方法 |
JP3217589B2 (ja) | 1994-04-28 | 2001-10-09 | 新日本製鐵株式会社 | 耐遅れ破壊特性に優れた高強度鋼棒およびその製造方法 |
CN1768155A (zh) | 2003-03-28 | 2006-05-03 | 株式会社神户制钢所 | 加工性优异的高强度弹簧用钢丝以及高强度弹簧 |
JP2006183137A (ja) | 2004-11-30 | 2006-07-13 | Nippon Steel Corp | 高強度ばね用鋼線 |
JP4116762B2 (ja) | 2000-09-25 | 2008-07-09 | 新日本製鐵株式会社 | 耐水素疲労特性の優れた高強度ばね用鋼およびその製造方法 |
US20080279714A1 (en) | 2004-11-30 | 2008-11-13 | Masayuki Hashimura | High Strength Spring Steel and Steel Wire |
CN100480411C (zh) | 2004-11-30 | 2009-04-22 | 新日本制铁株式会社 | 高强度弹簧用钢及钢线 |
WO2011093319A1 (ja) | 2010-01-26 | 2011-08-04 | 新日本製鐵株式会社 | 高強度冷延鋼板及びその製造方法 |
JP2012031462A (ja) | 2010-07-29 | 2012-02-16 | Jfe Steel Corp | 成形性および耐衝撃性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
EP2434028A1 (en) | 2009-05-15 | 2012-03-28 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hollow seamless pipe for high-strength springs |
EP2543747A1 (en) | 2010-03-04 | 2013-01-09 | Kabushiki Kaisha Kobe Seiko Sho | Seamless steel pipe of high-strength hollow spring |
JP2013076148A (ja) | 2011-09-30 | 2013-04-25 | Nippon Steel & Sumitomo Metal Corp | 引張強度980MPa以上の成形性に優れた溶融亜鉛めっき鋼板とその製造方法 |
JP2014019894A (ja) | 2012-07-17 | 2014-02-03 | Nippon Steel & Sumitomo Metal | 熱間成形鋼板部材およびその製造方法 |
JP2014043612A (ja) | 2012-08-27 | 2014-03-13 | Nippon Steel & Sumitomo Metal | 耐遅れ破壊特性に優れた高強度鋼材 |
JP2014118613A (ja) | 2012-12-18 | 2014-06-30 | Nippon Steel & Sumitomo Metal | 強度と耐水素脆性に優れたホットスタンプ成形体及びその製造方法 |
WO2014156187A1 (ja) | 2013-03-29 | 2014-10-02 | Jfeスチール株式会社 | 鋼材および水素用容器ならびにそれらの製造方法 |
-
2016
- 2016-03-10 BR BR112017012964-7A patent/BR112017012964A2/pt active Search and Examination
- 2016-03-10 KR KR1020177018324A patent/KR101922826B1/ko active IP Right Grant
- 2016-03-10 US US15/537,578 patent/US10752969B2/en active Active
- 2016-03-10 CN CN201680005101.5A patent/CN107109578B/zh not_active Expired - Fee Related
- 2016-03-10 EP EP16761816.4A patent/EP3222746A4/en not_active Withdrawn
- 2016-03-10 JP JP2017505392A patent/JP6338012B2/ja active Active
- 2016-03-10 WO PCT/JP2016/057564 patent/WO2016143850A1/ja active Application Filing
- 2016-03-10 MX MX2017008944A patent/MX2017008944A/es unknown
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3153072B2 (ja) | 1994-04-28 | 2001-04-03 | 新日本製鐵株式会社 | 耐遅れ破壊特性に優れた高強度鋼棒およびその製造方法 |
JP3217589B2 (ja) | 1994-04-28 | 2001-10-09 | 新日本製鐵株式会社 | 耐遅れ破壊特性に優れた高強度鋼棒およびその製造方法 |
JPH08311616A (ja) * | 1995-05-15 | 1996-11-26 | Sumitomo Electric Ind Ltd | 耐疲労性に優れたコイルばねとその製造方法 |
JPH09263876A (ja) * | 1996-03-29 | 1997-10-07 | Nippon Steel Corp | 遅れ破壊特性の優れた高強度機械構造用鋼およびその製造方法 |
JP2000256741A (ja) | 1999-03-09 | 2000-09-19 | Sumitomo Metal Ind Ltd | 熱間圧延棒鋼または線材の製造方法 |
JP2000256740A (ja) | 1999-03-09 | 2000-09-19 | Sumitomo Metal Ind Ltd | 熱間圧延線材の製造方法 |
JP4116762B2 (ja) | 2000-09-25 | 2008-07-09 | 新日本製鐵株式会社 | 耐水素疲労特性の優れた高強度ばね用鋼およびその製造方法 |
CN1768155A (zh) | 2003-03-28 | 2006-05-03 | 株式会社神户制钢所 | 加工性优异的高强度弹簧用钢丝以及高强度弹簧 |
CN100480411C (zh) | 2004-11-30 | 2009-04-22 | 新日本制铁株式会社 | 高强度弹簧用钢及钢线 |
JP2006183137A (ja) | 2004-11-30 | 2006-07-13 | Nippon Steel Corp | 高強度ばね用鋼線 |
US20080279714A1 (en) | 2004-11-30 | 2008-11-13 | Masayuki Hashimura | High Strength Spring Steel and Steel Wire |
EP2434028A1 (en) | 2009-05-15 | 2012-03-28 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Hollow seamless pipe for high-strength springs |
US20130037180A1 (en) | 2010-01-26 | 2013-02-14 | Nippon Steel Corporation | High-strength cold-rolled steel sheet and method of manufacturing thereof |
WO2011093319A1 (ja) | 2010-01-26 | 2011-08-04 | 新日本製鐵株式会社 | 高強度冷延鋼板及びその製造方法 |
EP2543747A1 (en) | 2010-03-04 | 2013-01-09 | Kabushiki Kaisha Kobe Seiko Sho | Seamless steel pipe of high-strength hollow spring |
JP2012031462A (ja) | 2010-07-29 | 2012-02-16 | Jfe Steel Corp | 成形性および耐衝撃性に優れた高強度溶融亜鉛めっき鋼板およびその製造方法 |
JP2013076148A (ja) | 2011-09-30 | 2013-04-25 | Nippon Steel & Sumitomo Metal Corp | 引張強度980MPa以上の成形性に優れた溶融亜鉛めっき鋼板とその製造方法 |
US20140377584A1 (en) | 2011-10-07 | 2014-12-25 | Jfe Steel Corporation | High-strength hot-dipped galvanized steel sheet having excellent formability and impact resistance, and method for producing same |
JP2014019894A (ja) | 2012-07-17 | 2014-02-03 | Nippon Steel & Sumitomo Metal | 熱間成形鋼板部材およびその製造方法 |
JP2014043612A (ja) | 2012-08-27 | 2014-03-13 | Nippon Steel & Sumitomo Metal | 耐遅れ破壊特性に優れた高強度鋼材 |
JP2014118613A (ja) | 2012-12-18 | 2014-06-30 | Nippon Steel & Sumitomo Metal | 強度と耐水素脆性に優れたホットスタンプ成形体及びその製造方法 |
WO2014156187A1 (ja) | 2013-03-29 | 2014-10-02 | Jfeスチール株式会社 | 鋼材および水素用容器ならびにそれらの製造方法 |
US20160053355A1 (en) | 2013-03-29 | 2016-02-25 | Jfe Steel Corporation | Steel material, hydrogen container, method for producing the steel material, and method for producing the hydrogen container (as amended) |
Non-Patent Citations (5)
Title |
---|
Chinese Office Action and Search Report for counterpart Chinese Application No. 201680005101.5, dated Apr. 28, 2018, with English translation of the Search Report. |
English language machine translation of JP-09263876-A to Yamazaki et al. Generated Jun. 25, 2019. (Year: 2019). * |
Extended European Search Report, dated Apr. 24, 2018, for corresponding European Application No. 16761816.4. |
International Search Report for PCT/JP2016/057564 dated Jun. 7, 2016. |
Written Opinion of the International Searching Authority for PCT/JP2016/057564 (PCT/ISA/237) dated Jun. 7, 2016. |
Also Published As
Publication number | Publication date |
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JPWO2016143850A1 (ja) | 2017-10-12 |
EP3222746A4 (en) | 2018-05-23 |
BR112017012964A2 (pt) | 2018-01-09 |
MX2017008944A (es) | 2017-12-07 |
JP6338012B2 (ja) | 2018-06-06 |
WO2016143850A1 (ja) | 2016-09-15 |
EP3222746A1 (en) | 2017-09-27 |
CN107109578A (zh) | 2017-08-29 |
KR101922826B1 (ko) | 2018-11-27 |
CN107109578B (zh) | 2019-11-05 |
US20180265940A1 (en) | 2018-09-20 |
KR20170090486A (ko) | 2017-08-07 |
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